Abstract
Greatly enhanced and abnormal Raman spectra were discovered in the nominal (Ba1 − xErx)Ti1 − x/4O3 (x = 0.01) (BET) ceramic for the first time and investigated in relation to the site occupations of Er3+ ions. BaTiO3 doped with Ti‐site Er3+ mainly exhibited the common Raman phonon modes of the tetragonal BaTiO3. Er3+ ions substituted for Ba sites are responsible for the abnormal Raman spectra, but the formation of defect complexes will decrease spectral intensity. A large increase in intensity showed a hundredfold selectivity for Ba‐site Er3+ ions over Ti‐site Er3+ ions. A strong EPR signal at g = 1.974 associated with ionized Ba vacancy defects appeared in BET, and the defect chemistry study indicated that the real formula of BET is expressed by (Ba1 − xEr3x/4)(Ti1 − x/4Erx/4)O3. These abnormal Raman signals were verified to originate from a fluorescent effect corresponding to 4S3/2→4I15/2 transition of Ba‐site Er3+ ions. The fluorescent signals were so intense that they overwhelmed the traditional Raman spectra of BaTiO3. The significance is that the abnormal Raman spectra may act as a probe for the Ba‐site Er3+ occupation in BaTiO3 co‐doped with Er3+ and other dopants. A new broad EPR signal at g = 2.23 was discovered, which originated from Er3+ Kramers ions. Copyright © 2014 John Wiley & Sons, Ltd.
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